CN102616803A - Preparation method of surface amino-modified mesoporous molecular sieve - Google Patents
Preparation method of surface amino-modified mesoporous molecular sieve Download PDFInfo
- Publication number
- CN102616803A CN102616803A CN2012100814975A CN201210081497A CN102616803A CN 102616803 A CN102616803 A CN 102616803A CN 2012100814975 A CN2012100814975 A CN 2012100814975A CN 201210081497 A CN201210081497 A CN 201210081497A CN 102616803 A CN102616803 A CN 102616803A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- solution
- dispersed
- amino groups
- surface amino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a preparation method of a surface amino-modified mesoporous molecular sieve, which comprises the following steps: by using diisocyanate molecules as a bridge, grafting the diisocyanate molecules through the reaction of Si-OH on the silicon dioxide molecular sieve surface and one uramido group in the diisocyanate diisocyanate, and grafting the amino group through the reaction of the other uramido group of the diisocyanate and one amino group in the ethylene diamine molecule, thereby finally obtaining the surface amino-modified mesoporous molecular sieve material. The preparation process can not damage the mesoporous orderliness of the molecular sieve, the pore sizes are uniformly distributed, and thus, the mesoporous molecular sieve can be used in the fields of catalysis, adsorption, separation and the like.
Description
Technical field
The present invention relates to a kind of preparation method of mesopore molecular sieve of surface amino groups modification, belong to mesoporous materials field.
Background technology
The researchist of Mobile company in 1992 is [Natrue first; 1992; 359,710] reported that the research of mesoporous material becomes one of research focus of material circle since the M41S series mesoporous material of high-specific surface area, high-sequential property; Synthesize the meso-porous molecular sieve material that different pore passage structures and hole dimension vary in size, had the mesopore molecular sieve of different surfaces texture property like MCM-41, MCM-48, HMS, MSU-X, SBA-15, SBA-16, MAS-7 etc.In recent years, mesopore molecular sieve is carried out the surperficial organic functionalization modified important research direction that becomes, like sulfydryl, carboxyl, sulfonic group, amino and organic hydrophobic modified.Amino gains great popularity as a kind of important functional organic group; Because it is amino positively charged easily and be basic group; Through interactions such as electrostatic force, hydrogen bonds; Help the fixing and absorption of guest molecules such as organic molecule, inorganic anion, protein, enzyme molecule and metals ion, thereby the catalysis of modulation molecular sieve and absorption property can be widely used in absorption and catalytic field.Silica mesoporous zeolite surface amino groups functionalization and modification has dual mode: cohydrolysis polycondensation and back grafting.Cohydrolysis polycondensation method is in the system of preparation mesopore molecular sieve; Directly add and contain amino organo-siloxane; Prepare the mesopore molecular sieve of surface amino groups modification through the cohydrolysis polycondensation mode in silicon source; But the mesoporous order of this method gained mesopore molecular sieve is not high, and functionalized amount is lower.Back grafting is through molecular sieve surface Si-OH and the organo-siloxane reaction that contains amino, thereby realizes the modification of mesopore molecular sieve surface amino groups, but the introducing earlier of this method-NH
2Form hydrogen bond easily with Si-OH, and then prevention Si-OH's is further amino modified.
Summary of the invention
The object of the invention is, solves above-mentioned existing existing problem, and the preparation method of the mesopore molecular sieve of the surface amino groups modification that a kind of surface amino groups content is high, amino is evenly distributed, mesoporous order degree is high is provided.
Technical scheme of the present invention is to utilize diisocyanate molecules to do " bridge "; Si-OH and the (NCO) reaction of a urea groups in the diisocyanate molecules through the SiO 2 molecular sieve surface; The elder generation grafting on diisocyanate molecules, utilize again vulcabond another urea groups (NCO) with quadrol (EDA) molecule in one-NH
2Reaction, amino in the grafting, obtain the meso-porous molecular sieve material of surface amino groups modification at last.
Preparing method of the present invention may further comprise the steps:
1, with 2-30 g vulcabond be dispersed in the 10-40 g toluene solution A; 5-30 g quadrol (EDA) is dispersed in must solution B in the 5-40 g ether.
2,1-5 g silicon-based mesoporous molecular sieve is joined in the step 1 gained solution A; Behind the 40-70 ℃ of stirring 2-48 h; Filtration obtains a white solid, with methylene dichloride the gained white solid is carried out after Suo Shi extracts 12-72 h, and 40-60 ℃ of vacuum-drying gets white powder.
3, get step 2 gained white powder 1-4g and join in the step 1 gained solution B, behind the stirring 4-48 h, filtration, 40-60 ℃ drying obtain the meso-porous molecular sieve material of surface amino groups modification under the room temperature.
Aforesaid vulcabond is a Ben Yajiaji vulcabond (XDI) or hexamethylene diisocyanate (HMDI).
Aforesaid silicon-based mesoporous molecular sieve is silica-based SBA-15 mesopore molecular sieve or MCM-41 mesopore molecular sieve or MCM-48 mesopore molecular sieve; The synthetic of them can be with reference to following document: J. Am. Chem. Soc. 1998,120,6024; J. Am. Chem. Soc. 1992,114,10834; Chem. Mater. 1998,10, and 3690; Angew. Chem. Int. Ed. 1996,35,1102; Science, 1995,267. 865.
The present invention compared with prior art has and is characterised in that:
1, the mesoporous order of molecular sieve is not produced destruction in the surface amino groups modifying process, pore size distribution is even;
2, the mesopore molecular sieve surface amino groups content height and the amino of the modification of gained surface amino groups are evenly distributed.
Embodiment:
The present invention combines following instance to be further described.
Embodiment 1
Get between 3 g Ben Yajiaji vulcabond (XDI) be dispersed in the 14 g toluene solution A.6 g quadrols (EDA) are dispersed in must solution B in the 5 g ether.The silica-based SBA-15 mesopore molecular sieve of 1.5 g is joined in the solution A, 40 ℃ stir 3 h after, cross and filter white solid, with methylene dichloride the gained solid is carried out after Suo Shi extracts 12 h, 50 ℃ of vacuum-dryings get white powder.Get this drying white powder 1g and join in the solution B, behind the stirring 5h, filtration, 40 ℃ of dryings obtain the SBA-15 meso-porous molecular sieve material of surface amino groups modification under the room temperature.
Embodiment 2
Get between 10 g Ben Yajiaji vulcabond (XDI) be dispersed in the 30 g toluene solution A.10 g quadrols (EDA) are dispersed in must solution B in the 20 g ether.The silica-based SBA-15 mesopore molecular sieve of 2 g is joined in the solution A, 60 ℃ stir 12 h after, cross and filter white solid, with methylene dichloride the gained solid is carried out after Suo Shi extracts 24 h, 40 ℃ of vacuum-dryings get white powder.Get this drying white powder 4 g and join in the solution B, behind the stirring 48h, filtration, 50 ℃ of dryings obtain the SBA-15 meso-porous molecular sieve material of surface amino groups modification under the room temperature.
Embodiment 3
Get 15 g1, hexamethylene-diisocyanate (HMDI) is dispersed in and gets solution A in the 35 g toluene.25 g quadrols (EDA) are dispersed in must solution B in the 15 g ether.The silica-based MCM-41 mesopore molecular sieve of 3 g is joined in the solution A, 60 ℃ stir 10 h after, cross and filter white solid, with methylene dichloride the gained solid is carried out after Suo Shi extracts 60 h, 60 ℃ of vacuum-dryings get white powder.Get this drying white powder 2 g and join in the solution B, behind the stirring 10h, filtration, 60 ℃ of dryings obtain the MCM-41 meso-porous molecular sieve material of surface amino groups modification under the room temperature.
Embodiment 4
Get between 20 g Ben Yajiaji vulcabond (XDI) be dispersed in the 20 g toluene solution A.20 g quadrols (EDA) are dispersed in must solution B in the 40 g ether.The silica-based MCM-41 mesopore molecular sieve of 4 g is joined in the solution A, 70 ℃ stir 24 h after, cross and filter white solid, with methylene dichloride the gained solid is carried out after Suo Shi extracts 36 h, 50 ℃ of vacuum-dryings get white powder.Get this drying white powder 3 g and join in the solution B, behind the stirring 36h, filtration, 55 ℃ of dryings obtain the MCM-41 meso-porous molecular sieve material of surface amino groups modification under the room temperature.
Embodiment 5
Get 7 g hexamethylene diisocyanates (HMDI) be dispersed in the 14 g toluene solution A.15 g quadrols (EDA) are dispersed in must solution B in the 15 g ether.The silica-based SBA-15 mesopore molecular sieve of 1.5 g is joined in the solution A, 50 ℃ stir 6 h after, cross and filter white solid, with methylene dichloride the gained solid is carried out after Suo Shi extracts 48 h, 50 ℃ of vacuum-dryings get white powder.Get this drying white powder 3 g and join in the solution B, behind the stirring 12h, filtration, 50 ℃ of dryings obtain the SBA-15 meso-porous molecular sieve material of surface amino groups modification under the room temperature.
Claims (6)
1. the preparation method of the mesopore molecular sieve of a surface amino groups modification is characterized in that, according to the following steps preparation:
A, with 2-30 g vulcabond be dispersed in the 10-40 g toluene solution A; With 5-30 g quadrol be dispersed in the 5-40 g ether solution B;
B, 1-5 g silicon-based mesoporous molecular sieve is joined in the step 1 gained solution A; Behind the 40-70 ℃ of stirring 2-48 h; Filtration obtains a white solid, with methylene dichloride the gained white solid is carried out after Suo Shi extracts 12-72 h, and 40-60 ℃ of vacuum-drying gets white powder;
C, get step b gained white powder 1-4g and join in the step a gained solution B, stir 4-48 h under the room temperature after, the meso-porous molecular sieve material that filter, 40-60 ℃ drying obtains the surface amino groups modification;
Aforesaid vulcabond is a Ben Yajiaji vulcabond or a hexamethylene diisocyanate;
Aforesaid silicon-based mesoporous molecular sieve is silica-based SBA-15 mesopore molecular sieve or MCM-41 mesopore molecular sieve or MCM-48 mesopore molecular sieve.
2. according to the preparation method of the mesopore molecular sieve of the said a kind of surface amino groups modification of claim 1, it is characterized in that, get between 3 g the Ben Yajiaji vulcabond be dispersed in the 14 g toluene solution A; With 6 g quadrols be dispersed in the 5 g ether solution B; The silica-based SBA-15 mesopore molecular sieve of 1.5 g is joined in the solution A, 40 ℃ stir 3 h after, cross and filter white solid, with methylene dichloride the gained solid is carried out after Suo Shi extracts 12 h, 50 ℃ of vacuum-dryings get white powder; Get this drying white powder 1g and join in the solution B, behind the stirring 5h, filtration, 40 ℃ of dryings obtain the SBA-15 meso-porous molecular sieve material of surface amino groups modification under the room temperature.
3. according to the preparation method of the mesopore molecular sieve of the said a kind of surface amino groups modification of claim 1, it is characterized in that, get between 10 g the Ben Yajiaji vulcabond be dispersed in the 30 g toluene solution A; With 10 g quadrols be dispersed in the 20 g ether solution B; The silica-based SBA-15 mesopore molecular sieve of 2 g is joined in the solution A, 60 ℃ stir 12 h after, cross and filter white solid, with methylene dichloride the gained solid is carried out after Suo Shi extracts 24 h, 40 ℃ of vacuum-dryings get white powder; Get this drying white powder 4 g and join in the solution B, behind the stirring 48h, filtration, 50 ℃ of dryings obtain the SBA-15 meso-porous molecular sieve material of surface amino groups modification under the room temperature.
4. according to the preparation method of the mesopore molecular sieve of the said a kind of surface amino groups modification of claim 1, it is characterized in that, get 15 g1, hexamethylene-diisocyanate be dispersed in the 35 g toluene solution A; With 25 g quadrols be dispersed in the 15 g ether solution B; The silica-based MCM-41 mesopore molecular sieve of 3 g is joined in the solution A, 60 ℃ stir 10 h after, cross and filter white solid, with methylene dichloride the gained solid is carried out after Suo Shi extracts 60 h, 60 ℃ of vacuum-dryings get white powder; Get this drying white powder 2 g and join in the solution B, behind the stirring 10h, filtration, 60 ℃ of dryings obtain the MCM-41 meso-porous molecular sieve material of surface amino groups modification under the room temperature.
5. according to the preparation method of the mesopore molecular sieve of the said a kind of surface amino groups modification of claim 1, it is characterized in that, get between 20 g the Ben Yajiaji vulcabond be dispersed in the 20 g toluene solution A; With 20 g quadrols be dispersed in the 40 g ether solution B; The silica-based MCM-41 mesopore molecular sieve of 4 g is joined in the solution A, 70 ℃ stir 24 h after, cross and filter white solid, with methylene dichloride the gained solid is carried out after Suo Shi extracts 36 h, 50 ℃ of vacuum-dryings get white powder; Get this drying white powder 3 g and join in the solution B, behind the stirring 36h, filtration, 55 ℃ of dryings obtain the MCM-41 meso-porous molecular sieve material of surface amino groups modification under the room temperature.
6. according to the preparation method of the mesopore molecular sieve of the said a kind of surface amino groups modification of claim 1, it is characterized in that, get 7 g hexamethylene diisocyanates be dispersed in the 14 g toluene solution A; With 15 g quadrols be dispersed in the 15 g ether solution B; The silica-based SBA-15 mesopore molecular sieve of 1.5 g is joined in the solution A, 50 ℃ stir 6 h after, cross and filter white solid, with methylene dichloride the gained solid is carried out after Suo Shi extracts 48 h, 50 ℃ of vacuum-dryings get white powder; Get this drying white powder 3 g and join in the solution B, behind the stirring 12h, filtration, 50 ℃ of dryings obtain the SBA-15 meso-porous molecular sieve material of surface amino groups modification under the room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100814975A CN102616803B (en) | 2012-03-26 | 2012-03-26 | Preparation method of surface amino-modified mesoporous molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100814975A CN102616803B (en) | 2012-03-26 | 2012-03-26 | Preparation method of surface amino-modified mesoporous molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102616803A true CN102616803A (en) | 2012-08-01 |
| CN102616803B CN102616803B (en) | 2013-11-27 |
Family
ID=46557089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100814975A Expired - Fee Related CN102616803B (en) | 2012-03-26 | 2012-03-26 | Preparation method of surface amino-modified mesoporous molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102616803B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403776A (en) * | 2014-12-15 | 2015-03-11 | 湖南科技大学 | Method for absorbing and regenerating waste lubricating oil |
| CN105367985A (en) * | 2015-11-18 | 2016-03-02 | 安徽雄亚塑胶科技有限公司 | TPE composition and high toughness EVA product prepared from TPE composition |
| CN105800703A (en) * | 2016-03-31 | 2016-07-27 | 任晓明 | Silicon dioxide modified nitrite removal material and preparation and regeneration method thereof |
| CN107522902A (en) * | 2017-06-08 | 2017-12-29 | 西北工业大学 | A kind of synthetic method of amination mesoporous silicon oxide for modified cyanic acid ester resin |
| CN114540978A (en) * | 2022-03-07 | 2022-05-27 | 百草边大生物科技(青岛)有限公司 | ES macrobio-fiber containing apigenin, luteolin and daidzein |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546568A (en) * | 2003-12-09 | 2004-11-17 | 太原理工大学 | Polyaminoester /molecular sieve composite material and its preparation method |
-
2012
- 2012-03-26 CN CN2012100814975A patent/CN102616803B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546568A (en) * | 2003-12-09 | 2004-11-17 | 太原理工大学 | Polyaminoester /molecular sieve composite material and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 赵会玲 等: "介孔材料氨基表面修饰及其对CO2的吸附性能", 《物理化学学报》, vol. 23, no. 6, 30 June 2007 (2007-06-30), pages 802 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403776A (en) * | 2014-12-15 | 2015-03-11 | 湖南科技大学 | Method for absorbing and regenerating waste lubricating oil |
| CN105367985A (en) * | 2015-11-18 | 2016-03-02 | 安徽雄亚塑胶科技有限公司 | TPE composition and high toughness EVA product prepared from TPE composition |
| CN105800703A (en) * | 2016-03-31 | 2016-07-27 | 任晓明 | Silicon dioxide modified nitrite removal material and preparation and regeneration method thereof |
| CN105800703B (en) * | 2016-03-31 | 2018-12-21 | 任晓明 | A kind of silica modified nitrite removal material and its preparation regeneration method |
| CN107522902A (en) * | 2017-06-08 | 2017-12-29 | 西北工业大学 | A kind of synthetic method of amination mesoporous silicon oxide for modified cyanic acid ester resin |
| CN114540978A (en) * | 2022-03-07 | 2022-05-27 | 百草边大生物科技(青岛)有限公司 | ES macrobio-fiber containing apigenin, luteolin and daidzein |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102616803B (en) | 2013-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102616803B (en) | Preparation method of surface amino-modified mesoporous molecular sieve | |
| Pang et al. | Design of aminopolymer structure to enhance performance and stability of CO2 sorbents: poly (propylenimine) vs poly (ethylenimine) | |
| Li et al. | Influence of silica types on synthesis and performance of amine–silica hybrid materials used for CO2 capture | |
| Sayari et al. | CO2-induced degradation of amine-containing adsorbents: reaction products and pathways | |
| Vinu et al. | Biomaterial immobilization in nanoporous carbon molecular sieves: influence of solution pH, pore volume, and pore diameter | |
| Fu et al. | Scalable fabrication of electrospun nanofibrous membranes functionalized with citric acid for high-performance protein adsorption | |
| Li et al. | Core–shell metal–organic frameworks as the mixed-mode stationary phase for hydrophilic interaction/reversed-phase chromatography | |
| Yoo et al. | Engineering nanospaces: OMS/dendrimer hybrids possessing controllable chemistry and porosity | |
| Mulik et al. | Cross-linking 3D assemblies of nanoparticles into mechanically strong aerogels by surface-initiated free-radical polymerization | |
| Mondal et al. | Bovine serum albumin adsorption on gluteraldehyde cross-linked chitosan hydrogels | |
| Zhang et al. | Gas phase synthesis of aminated nanocellulose aerogel for carbon dioxide adsorption | |
| Zhu et al. | Superinsulating polyisocyanate based aerogels: a targeted search for the optimum solvent system | |
| KR20120124412A (en) | Specific sorbent for binding proteins and peptides, and separation method using the same | |
| Zhang et al. | Facile preparation of titanium (IV)-immobilized hierarchically porous hybrid monoliths | |
| Duman et al. | Kinetic and thermodynamic properties of purified alkaline protease from Bacillus pumilus Y7 and non‐covalent immobilization to poly (vinylimidazole)/clay hydrogel | |
| Nguyen et al. | Enhanced protein adsorption capacity of macroporous pectin particles with high specific surface area and an interconnected pore network | |
| Lunn et al. | Peptide Brush Ordered Mesoporous Silica Nanocomposite Materials | |
| CN105080367B (en) | A kind of composite nanometer filtering film containing composite nanoparticle and preparation method | |
| Wan et al. | Functionalized periodic mesoporous organosilicas for enhanced and selective peptide enrichment | |
| Liu et al. | Hierarchically porous covalent organic framework for adsorption and removal of triphenylmethane dyes | |
| Liu et al. | Mesocellular silica foam supported polyamine adsorbents for dry CO2 scrubbing: Performance of single versus blended polyamines for impregnation | |
| Lim et al. | Influences of diatom frustule morphologies on protein adsorption behavior | |
| Yang et al. | Synthesis of a novel molecularly imprinted organic–inorganic hybrid polymer for the selective isolation and determination of fluoroquinolones in tilapia | |
| Johnson III et al. | Mineralization of clay/polymer aerogels: a bioinspired approach to composite reinforcement | |
| Liang et al. | Direct preparation of porous cellulose microspheres via a self-growth process on bamboo fibers and their functionalization for specific adsorption of histidine-rich proteins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131127 Termination date: 20160326 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |